CH628360A5 - Process for the preparation of a terpolymer containing ester and amide bonds between the monomer units - Google Patents

Description

The present invention relates to a method for producing a terpolymer with ester and amide bonds between the monomer units. The terpolymers are lac-tam-polyol-polyacyllactam terpolymers or lactam-polyol-acylpolylactam terpolymers with preferably up to 100% ester end groups.

Polyamides include a broad class of polymers with a wide range of properties. Many polyamides have excellent combinations of properties for special applications. An important class of polyamides are those by the polymerization of lactams such as caprolactam and the like. manufactured polylactams. Polycaprolactam, better known as Nylon 6, is the most widely used polycaprolactam because of its excellent mechanical and physical properties and its low price. Because of the many desirable properties of polylactams, polylactams other than polycaprolactam are considerably

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

3rd

628 360

Bulk has been used when nylon 6 was unsuitable for some special end uses. Nylon 12 made from lauryl lactam or 12-aminododecanoic acid is an example of such a polymer. This polymer is characterized by lower water absorption and consequently better dimensional stability and better electrical properties than nylon 6. Nylon 12 is also more flexible and has a lower melting point than nylon 6.

For still other applications, a polyamide with higher water absorption combined with greater elasticity than nylon 6 would be useful for a number of applications. Some nylon copolymers are known to provide the features just mentioned. Polyamide-polyether copolymers are known to have a combination of properties that make them suitable as fibers, fabrics, films, and molded articles. It is also known that lactam-polyol copolymers can be made by base catalysis of lactams in the presence of polyalkylene glycols or other polymerizable polyol intermediates using isocyanate initiators, e.g. as described in ÜS-PS No. 3 320 335. This polymerization method gives block copolymers with a number of good properties at a reasonable cost. One of the main disadvantages of the polylactam-polyether copolymers produced by this method is their low heat resistance.

The polymerized lactam component of the terpolymer according to the invention is made from cyclic monomeric lactams of the formula

Vnik formed in which Y represents an optionally substituted alkylene group having at least 3, preferably 3 to 12 or 14 and more preferably 5 to 11 carbon atoms.

A preferred monomer is e-caprolactam. Other suitable lactams are 2-pyrrolidone, 2-piperidone, Capryllac-tam, Lauryllactam and. The like. In addition to the lactams unsubstituted in their carbon chain, lactams with substituents in the carbon chain which do not hinder or otherwise adversely affect the polymerization are also included.

During the polymerization, the lactam ring is opened to form the following monomeric unit.

O

II

-C-Y-NH-

which together with other lactam molecules form a polymeric block of the formula

O

II

- (C-Y-NH) X-

in which x is an integer greater than 1. The monomeric lactam unit can also react with a polyacyllactam. Thus, a polylactam block connected to a polyacyllactam forms a polymer section of the formula

O

II

- (C-Y-NH) X — A — R- (A ') y—

in which R is a hydrocarbon group described below, A and A 'acyl groups, x is a larger integer than 1 and y is 1 or a larger integer.

The monomeric lactam unit can also react with the acyl polylactam. Thus, a polylactam block bonded to an acyl polylactam forms a polymer section of the formula q q

II II

- (C — Y — NH) X — X— (NH — Y-C) y—

in which X is an acyl group, x is a larger integer than 1 and y is 1 or a larger integer.

Third, in the course of the polymerization of the components described above, a polyol can react with a polymerizable lactam unit or a lactam block to form a polymer section of the formula

O

II

- (O — Z) z — O— (C — Y — NH) X—

form in which Z is an optionally substituted or acylated hydrocarbon group which, together with the oxygen atom, forms a polyether or polyester section of a polymeric molecule and x and z are integers and at least 1.

The optionally substituted or acylated hydrocarbon group Z can be of any size; however, it is preferably limited to about 6 carbon atoms. Rather preferred are unsubstituted aliphatic groups such as methylene, ethylene, propylene, butadienylene and the like. Other suitable Z groups include phenylene, chlorophenylene, tolylene, isobutylene, isopropylene, ethyl carbonyl, propyl carbonyl, ethyl sulfonyl, propyl thiocarbonyl and the like. the like

The abovementioned preference for unsubstituted aliphatic Z groups means that terpolymers which have polyether sections are preferred over other versions with polyester sections.

The fourth, optional reaction component is a monofunctional alcohol, which can be added at any time before or simultaneously with the addition of the polymerization catalyst. Suitable alcohols for the preparation of terpolymers having at least partial ester end groups are alcohols with only one hydroxyl group, such as e.g. Methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-ethylhexanol, 1-dodecanol, 1-octadecanol, 2-octanol, 1-decanol and isomers or mixtures thereof. Unsaturated alcohols (e.g. allyl alcohol), nitro alcohols, amino alcohols (e.g. dimethylamino ethanol) and the like. are also considered suitable. Other suitable monofunctional alcohols can be selected from polymers having a hydroxyl group; Examples are tridecanol ethylene oxide condensates (polyoxyethylene). In addition to the alcohols listed, monofunctional alcohols which do not dehydrate easily are also desirable. Aromatic alcohols such as phenol, cresol etc. are not suitable, however aromatic residues can be present on the carbon chain of the aliphatic alcohols.

The monofunctional alcohol is preferably one that is soluble in the lactam polymerization system, and the application of the alcohol varies considerably depending on the desired nature of the end product. The alcohol can vary from about 0.1 to 150% of the molar equivalents of the excess imido groups of the acyl polylactam or polyacyl lactam, the excess being based on the molar equivalents of the hydroxyl groups of the polyol present in the reaction mixture.

The number of acyllactam groups, i.e. H. Imido groups, in excess with respect to the hydroxyl groups contributed by the polyol, determine the number of end groups in the terpolymer and thus also the amount of necessary monofunctional alcohol. Depending on the presence of the alcohol in the reaction mixture, the terpolymer becomes about 0.1

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

628 360

4th

have up to 100% ester end groups. The presence of the alcohol in the reaction mixture creates conditions where the alcohol reacts with the imide to form ester groups; however, this reaction occurs very slowly in the absence of the basic lactam polymerization catalyst. In order to achieve a terpolymer with at least partial ester end groups, the presence of the lactam polymerization catalyst is necessary both for the ester formation and for the formation of the terpolymer.

The preferred polymerization temperatures of this system are about 90 to 190 ° C, especially about 120 to 180 ° C. Under these conditions, the monofunctional alcohol reacts very slowly with the imide to form ester groups. In the presence of the lactam polymerization catalyst, however, the ester formation takes place very quickly according to one embodiment of this invention.

In preferred aspects of this invention, it is theoretically believed that the lactam in the polymer is in the form of polylactam blocks that alternate with polyol blocks. The polylactam blocks can be of any size; however, they usually have a molecular weight of at least about 500 and preferably at least about 1000.

The polymerized polyol components of the terpolymer according to the invention are formed from polyol intermediates with at least two hydroxyl groups. Within the scope of the above class, a large number of suitable compounds are included, which range from simple diols such as ethylene glycol to complex polyols such as poly (£ -caprolactone) diol. Examples are alkylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, tetramethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-hexanediol, 1,5-pentenediol, butylene glycol, 1,4-butanediol, dicyclopentadiene glycol glycol and isopropylidene-bis- (p-phenyleneoxypropanol-2); also diols other than alkylene glycols such as hydroxyethyl acrylate and hydroxypropyl methacrylate; also polyols with more than two hydroxyl functions such as glycerol, pentaerythritol, 1,2,6-hexanetriol and 1-trimethylolpropane; furthermore polymeric polyols such as polyethylene glycols, polypropylene glycols, polyoxypropylene diols and triols, polytetramethylene glycols, castor oils, polybutadiene glycols and polyester glycols; and also a large number of compounds which have substituents other than hydroxyls, such as e.g. 2,4-dichlorobutylene glycol.

If the polyol intermediate is a polymer, the molecular weight can be of any size. Commercial polyols have a molecular weight of 200 to 5000, but polyols outside of this range are also useful in the practice of the invention.

The third component of the terpolymer according to the invention has the following configuration in the polymer chain

- (A ~ R) "- (A ') y—

in which R is a hydrocarbon group, A and A 'acyl groups, y is an integer and at least 1 and n is 0 or 1. The R group can be any hydrocarbon group that has at least two valence bonds to link to the acyl groups shown in the formula. Examples are functional groups which are removed by removing hydrogen atoms from methane, ethane, propane, hexane, dodecane, benzene, toluene, cyclohexane and the like. were obtained. The R group can be of any size; however, it is preferably limited to approximately 20, in particular approximately 8, carbon atoms. If the integer y is 1, the link is a diacyl group. The A groups are preferably o SO o

M II II U

-C-, -C-, -S-, or -P-

u «

O

Groups. Among the groups listed above, the car bonyl groups are most preferred.

The values for y have a direct relationship to the thermoplasticity of the terpolymer. The higher the value of y, the more cross-linked the finished polymer will be. The values for y can be as high as 6 or 8, but preferably do not exceed 2 or 3. However, when n is zero and A 'is an acyl group, e.g. a phosphoryl group il

-P-

I.

there will be another group attached to the phosphorus atom besides the two amide groups. The additional group can either be another amide group or an atom, e.g. Hydrogen and halogen, or a monovalent hydrocarbon radical. If A 'is a carbonyl group

O

-C-

represents, only two amide groups are bonded to the carbonyl.

The polymerized product containing the above-mentioned components can have a number of different structures depending on the process conditions and the relative proportions of the reaction components. Polymers can be produced with relatively small sections of lactam units, which are connected to sections of polyol units of equal length via the polyacyls described. Or large sections of a polymeric component can be connected to a larger number of small sections of another polymeric unit, the small sections being linked to one another and to the other type of polymeric component by polyacyls or acyls. Or sections of different sizes from the lactam and polyol polymer units can be combined by the polyacyl components to form highly random terpolymers.

Another form of polymer within the scope of this invention are block polymers, where moderately large blocks or sections of the lactam and polyol polymer units are alternately arranged in the polymer chain and connected by the polyacyl or acyl groups. If the polyacyl or acyl linkage is considered to be part of either the lactam or polyol block for simplicity, then the block polymers can be expressed as two alternating blocks labeled A and B, rather than in terms of complicated patterns of A, B and C denoted blocks. The block polymers according to the invention have three general structural configurations AB, ABA and a repeating pattern of AB sections. Following a general characterization of the polymers, it should be recognized that the exact structural configuration may differ somewhat from the general characterization. To illustrate, a theoretical formula for a repeating AB type lactam-polyol-polyacyllactam or lactam-polyol-acylpolylactam block terpolymer could be the following

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

5

628 360

O O

"o o o"

"I,"

{N- [(C-Y-NH) -A-R-A {NH-Y-C) t- (0-Z) -O] -A-R-A (NH-Y-C) ,, - N; VYy x X1 zwx Vyy in which R and Z are divalent hydrocarbon groups, Y To explain a theoretical formula for an alkylene group with at least 3 carbon atoms, A lactam-polyol-acylpolylactam block terpolymer of itself and A 'acyl groups and x, x' , x ", z and w 1 or larger repeating AB type which are the following are integers. io

O O

"0 0 0" •

/ "c \ h h f C v

I N- [(CY-NH) - (NH-YC) (OZ) -O] -X- (NH-YC) -N} \ Y / X xz * x in which Z is a divalent hydrocarbon group, Y is an alkylene group at least 3 carbon atoms, X is an acyl group, and x, x ', x ", z and w are 1 or greater whole 20 numbers.

0 o ti tl

R'-O- {(CY-NH) - (AR) -A '- (NH-YC) X nx in which R and Z are divalent hydrocarbon groups, Y is an alkylene group with at least 3 carbon atoms, A and A' acyl groups, R ' an optionally substituted aliphatic hydrocarbon group in which the ester group is not bound to a cyclic or aromatic radical, where R 'corresponds to the radical R in the monofunctional alcohol ROH used, x, x', x ", z and w 1 or larger integers and n mean 0 or 1.

For example, when Y is a straight chain amylene group, 35 A and A 'carbonyl groups, Z is an ethylene group, and R is a phenylene group, the terpolymer is a caprolactam-ethylene glycol polymer where the caprolactam portions of the polymer are with one another and with the ethylene glycol portions are linked by terephthaloyl bonds. 40 Other lactam-polyol polymers of AB, AB A as well as of the repeating AB type are immediately recognizable for the person skilled in the art from what has been developed here.

If the polymers according to the invention are of the ABA type, where a block of one type of the polymer section 45 is arranged between two blocks of the other type of the polymer section, the polymer can either be of the polyol-lactam-polyol type or Lactam-polyol-lactam type. The latter type of ABA polymer is preferred.

If the lactam-polyol-polyacyl-lactam or lactam-50 polyol-acylpolylactam polymer is a block polymer, the polyol blocks, like the polylactam blocks, can be of any size; however, they usually have a molecular weight of at least about 500, preferably at least about 1000. The ratio of the number of lactam blocks to the number of 55 polyol blocks can also vary. Because the block polymers can be of any of the types labeled AB, ABA, or repeating AB, the ratio of the lactam blocks to the polyol blocks can vary from 2: 1 to 1: 1 to 1: 2. Mixtures of two or more block polymers with different ratios of the lactam blocks to the polyol blocks give ratios of the polymer blocks that lie between those given above.

In the theoretical formula above for a lac-tam-polyol block terpolymer, the polyacyl linkage 6S is shown as being arranged between two lactam-polymer sections and also between a polyether section and a lactam-polymer section . Be in practice

Another theoretical formula for illustrating a lactam-polyol-polyacyllactam or lactam-polyol-acylpoly-lactam block terpolymer of the repeating AB type could be the following

O

[OZ) -O] - (AR) -A (NH-YC) "-0-R 'between the polyacyl or acyl linkages are occasionally also arranged between two polyol blocks. It should also be noted that the polyacyl or acyl linkages between lactam and polyol blocks do not always have to be present, because the necessary ester bond can also be produced by the oxygen atom of the polyether section and the carbonyl group of the polylactam section.

As mentioned earlier, the terpolymers according to the invention are characterized by the presence of ester and amide bonds between the sections of the polymer. The term "section" includes both simple units such as

II Ii

-C- (CH2) s-NH- and -C-NH-

as well as blocks of several units, e.g.

O

II

[-C— (CH2) s-NH—] x understood.

The molecular weight of the terpolymers can vary widely from a number average molecular weight of just a few thousand to a million or higher. For thermoplastic, uncrosslinked polymers, a preferred range is about 10,000 to 200,000. If the polymers are crosslinked, the molecular weight can be much higher and in the range of 100,000 to several million.

When block polymers are formed, the molecular weight of the polyol blocks is an important factor in the selection of preferred polymers according to the invention. Polyol blocks with a number average molecular weight of about 500 or 600 generally have a tendency to have particularly good low temperature properties. This minimum molecular weight level for the polyol blocks is subject to some variations in that low temperature properties also depend on the degree of block polymerization, the nature of the block polymer, i.e. AB, ABA or repeating AB, the ratio of the lactam content to the polyol content and the specific lactam and polyol present in the polymer can be determined. In view of the maximum molecular weight

628 360

6

important to the polyol blocks, the preferred polyols have a maximum number average molecular weight of about 6000, in particular about 4000. Above these sizes, the polyol prepolymers tend to have a reduced hydroxyl function, which makes it more difficult to incorporate the polyol into the polymer .

The terpolymers according to the invention have a wide range of properties which can be adapted to be specially tailored for a specific end use. In addition to the crosslinking, adaptation of the polymer structure and the molecular weight of the polymer blocks, other means of changing the properties can also be used. The crystallinity of the polymers, which may be present in the lactam sections of the polymers, can be increased or decreased by changing the polymerization temperature. Because every crystallinity in the terpolymers according to the invention is largely present in the lactam sections of the polymer, a change in the lactam content of the polymer can also cause a change in the crystallinity. Polymers with relatively high crystallinity tend to be rigid, rigid polymers, while those with little or no crystallinity tend to be more elastic in nature.

As mentioned earlier, the type of lactam, polyol and polyacyllactam or acylpolylactam can also affect the properties of the final polymer. Polyethylene glycol sections tend to produce polymers with high water absorbency, while polypropylene glycol or polytetramethylene glycol sections provide polymers with comparatively low water absorbency. As another example, caprolactam polymer sections in the terpolymer according to the invention provide stronger and stiffer polymers than the homologous polymers, the sections of a higher lactam, e.g. Capryllactam or dodecanollactam. Regarding the polyacyllactam or acylpolylactam, an aromatic hydrocarbon group between the acyllactam groups produces a stiffer terpolymer than a long chain aliphatic group. Even more importantly, the use of an acyl-bis-lactam gives an essentially linear polymer (with glycols), while the use of acyl-tris or tetra-kis-lactams results in a branched or cross-linked terpolymer. In the same way, an acyl-bis-lactam can be used to produce a branched or cross-linked polymer by using polyols with more than two hydroxyl groups.

With all the possibilities mentioned for modifying and adapting the properties of the terpolymers according to the invention, it can be seen that the terpolymers are useful for a large number of uses. One of these uses is textile fiber. The terpolymers possess properties that make them useful as textile fibers over the entire ratio range of the components, from polymers with very little polyether content to those with a large amount. In addition to adding only the single component of the textile fiber, the terpolymers can also be part of a composite or conjugated fiber. It is contemplated that conjugated nylon and terpolymer fibers are particularly useful for a number of textile applications and other applications. Other textile applications for the terpolymers include their use in the fabrication of nonwovens and highly moisture absorbent fibers. The terpolymers can also be processed into foamed articles, either during or after their polymerization. Rigid or flexible foam products can be produced. Because of their direct production from the monomeric components, the terpolymers can be in large form, e.g.

Furniture and furniture components and automotive parts. The terpolymers can also be produced in the form of casting resins, which can then be molded by injection molding, extrusion, thermoforming or technology to give products of any shape. The more highly elastic compositions can be used in the manufacture of car tires and tire components. The terpolymers can also be provided with fillers, fibers, pigments, dyes, stabilizers, plasticizers, flame retardants and other modifiers in order to change their properties and thereby increase the scope of their applicability even further. One of these modifications involves reinforcing the terpolymer with fillers and fibers that have been treated with a coupling agent that is capable of strengthening the binding of the filler or fiber to the polymer molecules. A large number of organosilane compounds have been found which are able to solve the task of improving the adhesion between polymer and filler or fiber. Examples of suitable grganosilane couplers for use with the terpolymers according to the invention are 3-aminopropyltriethoxysilane, glycidoxypropyltrimethoxysilane and N-trimethoxysilylpropyl-N - /? - aminoethylamine. Preferred fillers and fibers are quartz, wollastonite, feldspar, calcined kaolin earth, glass fibers and other high-performance fibers such as graphite, boron, steel fibers and the like. The concentration of fillers and fibers can vary from very small amounts such as 1 or 2 volume percent to 70 or 80 volume percent or more.

The production process for the terpolymers is characterized in that (a) a lactam monomer, (b) a polyol and (c) a polyacyllactam or acylpolylactam of the formula:

r 1 f I f \

C-Y-N- (A-R) -f-A '-N-Y-C \ (1) ti n I »I

0 \ O / y wherein A and A 'are acyl groups of the formula:

0

S

0

0

1!

1!

II

T1

-c-s

-C-,

-S-,

11

0

-s-

or a divalent phosphorus-containing acyl group, the two free valences of which are bonded to the same pentavalent phosphorus atom which is bonded to an oxygen atom by a double bond, Y denotes an alkylene group with at least 3 carbon atoms, R denotes a hydrocarbon group, y denotes an integer is at least 1 and n is 0 or 1, in the presence of a basic lactam polymerization catalyst, the amount of polyol being 10 to 90% by weight.

The polymerization temperatures can vary from the melting point of the lactam or lower to the melting point of the resulting polymer or higher. Depending on the particular ingredients used, these temperatures can range from 70 to 230 ° C or higher. Preferred temperatures are about 90 to 190 ° C, especially about 120 to 180 ° C for caprolactam terpolymers. Even more preferred is a polymerization where the temperature is increased during the polymerization at the beginning from an initial temperature of about 70 to 100 ° C to a final temperature of about 150 to 180 ° C. Such a technique produces rapid polymerization and gives a terpolymer with high tensile strength and high modulus.

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

7

628 360

The time required for complete polymerization will vary considerably depending on the polymerization temperature and the specific components used in the polymerization process. The total polymerization time can be as little as 30 seconds or less, but preferably 1 to 10 minutes, and can be extended to any period up to a few days or more. In general, polymerization times of 1 to 10 minutes are preferred for most polymerization systems.

The lactam and polyol used in the polymerization have been described in detail above. The lactam polymerization catalyst useful here includes that class of compounds that are commonly recognized as suitable basic catalysts for the anhydrous polymerization of lactams. In general, all alkali or alkaline earth metals are effective catalysts, either in the metallic form or in the form of hydrides, halohydrides, alkyl halides, oxides, hydroxides, carbonates and the like.

Also useful are a number of organometallic compounds of the above-mentioned metals such as metal alkyls, phenyls, amides and the like. Examples are sodium hydride, potassium hydroxide, lithium oxide, ethyl magnesium bromide, calcium fluorohydride, strontium carbonate, barium hydroxide, methylnutrium butyllithium, potassium phenyl, diphenyl barium, sodium amide and magnesium diethyl. All of the aforementioned compounds react with the lactam monomer to form the metal lac-tam, which is the active catalyst in the lactam polymerization. The metal lactam catalyst can therefore by reacting one of the above metals or a metal compound with lactam monomer in the polymerization medium in situ or by prior reaction of the

Metal or the metal compound are formed with a stoichiometric quantity of the lactam monomer. Examples of metal lactam catalysts are sodium caprolactam, magnesium caprolactam, bromagnesium pyrrolidone and chloro-calcium caprolactam. The catalyst concentration can vary from a fraction of one mole percent to 15 or 20 or more mole percent of the lactam monomer to be polymerized.

The polyacyl as well as the acyl bonds or linkages are incorporated into the polymer chain by reacting the polyacyllactam or acylpolylactam with the lactam and polyol component. In the presumed formula for the polyacyllactams useful herein, the R group can be any hydrocarbon group with the necessary number of 15 valences available to bind all of the acyl groups involved in the compound to themselves. The hydrocarbon group can be of any size; however, it preferably contains a maximum of 8 to 10 carbon atoms. Examples of useful R groups are phenylene, bipheny-2o len, methylene, hexylene, tolylene and analogous hydrocarbon groups with more than two sites available for binding the acyl groups. The integer y is preferably 1 to 3, The A and A 'groups are carbonyls, thiocarbonyls, sulfonyls, sulfoxides or phosphoryls. A and A 'may be the same or different. Y can represent an alkylene chain of 3 to 14 or more, preferably 3 to 10 carbon atoms. In the class of polyacyllactams, which are included in the formula given above, preference is given to those where A and A 'are carbonyl groups. Those compounds are particularly preferred where A and A 'are carbonyls, R is either alkylene or phenylene, Y is a five-membered alkylene chain and y is 1.

Examples include terephthaloyl-bis-caprolactam, i.e. H.

O 0 0 O

Il II / ——n H

C ~ CH2 ~ CH2 "CH2 ~ CH2 ~ CH2" N_C /) ~ C -n ~ CH2 "CH2" CH2 ~ CH2 "CH2 ~ C

Adipoyl-bis-lactam, malonyl-bis-pyrrolidone, succinoyl-bis-pyrrolidone, glutaroyl-bis-piperidone, glutaconoyl-bis-piperi-don, 2-ethyl-2-phenylglutaroyl-bis-valerolactam, 2.3-diethyl-succinoyl- bis-caprolactam, pimeloyl-bis-capryllactam, seba- 45 coyl-bis-caprolactam, phthaloyl-bis-piperidone, isophthaloyl-bis-dodecanolactam, 1.2.5-benzenetricarbonyl-tris-caprolactam, 1.2.3.4-naphthalenetetracarbonyl-tetrakis and 1,4-cyclohexanedicarbonyl-bis-caprolactam; further 1,3-benzenedisulfonylcaprolactam, 3- (sulfonylcaprolactam) -benzoylcapro-50 lactam, phosphoryl-tris-caprolactam, benzene-phosphoryl-bis-caprolactam and dithioterephthaloyl-bis-caprolactam.

The amount of the polyacyllactams or acyl polylactams required for the preparation of the terpolymers according to the invention depends on the amounts of the lactam and 55 polyols used. For preferred polymerizations it is desirable to

that the polyacyllactam or acylpolylactam is present in amounts of about 100 to 500, preferably about 100 to 200 equivalent percent of the polyol. If the polyacyllactam or acylpolylactam is present in a smaller amount than a molecular equivalent based on 60 of the polyol, a polyol prepolymer is formed, but the subsequent lactam polymerization is very slow. In those preferred polymerization systems where the polyacyllactam or acylpolylactam concentration exceeds the stoichiometric amount equivalent to the polyol 65, the excess may be from 0.01 to about 30 or more mole percent of the lac-tam monomer. A preferred range is approximately

0.1 to 10 mole percent, especially about 0.2 to 5 mole percent of the lactam monomer.

The lactam and polyol can be present in different proportions. The preferred ratio depends on the intended use of the finished terpolymer. For end uses that require a strong, rigid material, the lactam content of the polymerizable medium should be relatively high, e.g. 60 or 80% by weight. For other uses where the elastic properties such as high elongation or where water absorption is desirable, the proportions of the two monomers may be reversed so that the polymerizable medium contains up to 90% by weight of the polyol compound. Polymers containing approximately equal amounts of lactam and polyol are preferred for quite a number of uses because of the advantageous combination of properties achieved with such polymers.

example 1

2100 g of e-caprolactam is heated in vacuo to remove the water. Heating is continued until 100 g of caprolactam are removed from the reaction vessel. The caprolactam is then allowed to cool, after which 725 ml of pyridine are added. Then the mixture is allowed to cool again to about 40 ° C, after which time 609 g of terephthaloyl chloride are added at a rate sufficient to keep the vessel temperature at about 80 to 90 ° C

628 360

8th

to keep. The mixture is then heated to 135 to 140 ° C for two hours. After this time, the resulting solution is poured into 14 liters of ice water to precipitate the terephthala-loyl-bis-caprolactam. The precipitate is filtered and washed three times with cold water and once with methanol. After washing, the powder is dried at 50 ° C.

Seven different caprolactam-polypropylene glycol-terephthaloyl-bis-caprolactam terpolymers are made using the ingredient amounts shown in the table below.

In all of the following tables, the quantities of constituents listed and used in various polymerization systems are expressed as parts by weight.

Table I

material

A

B

C.

D

E

F

G

"Pluracol 2010"

328.4

281.1

163.6

186.5

97.3

64.2

31.1

Caprolactam

104.0

169.0

157.0

279.0

234.0

273.0

312.0

Terephthaloyl-bis-caprolactam

51.5

49.7

29.3

34.0

18.3

12.8

7.3

"Santowhite Powder" *

1.0

1.0

0.7

1.0

0.7

0.7

0.7

% By weight glycol in the copolymer

68

56

47

37

28

18th

9

* Polypropylene glycol with a molecular weight of 2000. ** Antioxidant, 4,4'-butylidene-bis- (6-tert-butyI-m-cresol).

In each of the above approaches, the polypropylene glycol, caprolactam, "Santowhite powder" and terephthaloyl-bis-caprolactam are mixed at 100 ° C. Bromagnesium pyrrolidone is added to the resulting solution in an amount which gives 8 millimoles of bromagnesium pyrrolidone per mole of caprolactam. Then the reaction mixture is heated to 100 ° C. and varies between 3 and 13 mm

25th

Cast thick film form. The mold is brought to 160 ° C within 12 minutes. After 30 minutes, the mold is opened and the finished, polymerized composition is removed. Samples of each composition are tested to determine their mechanical properties, which are listed in Table II.

Table II

Terpolymer

train

Tear

print

Blow

Strength, kg / cm2

strength

Permanent deformation toughness

Flow

fracture

% Strain

Module kg / cm2

stress

R.T.

100 ° C

kg / cm / cm

Point

in the event of breakage

25%

score

A - 68% pluracol

91

372

25th

39

56

85

B - 56% pluracol

150

527

29

45

92

C - 47% pluracol

274

505

38

183 -

33

64

D - 37% Pluracol

373

493

56

316

42

67

E - 28% pluracol

429

450

70

485

52

62

F - 18% pluracol

450

429

285

92

759

69

63

G - 9% Pluracol

668

548

35

87

801

60

60

10.33

Polycaprolactam

759

555

50

15 475

6.0

Example 2

Seven different caprolactam-polytetramethylene glycol uses of the Be-coI-terephthaloyl-bis-caprolactam terpolymers given in the table below are produced with partial quantities.

Table III

material

A

B

C.

D

E

F

G

"Polymeg" *

229.0

196.0

163.0

130.0

97.0

64.0

31.0

Caprolactam

79.0

117.0

156.0

- 195.0

- 234.0

273.0

311.0

TBC "

42.5

36.7

30.9

25.1

19.3

13.4

7.6

"Santowhite Powder"

0.7

0.7

0.7

0.7

0.7

0.7

0.7

% By weight glycol in the copolymer

65

56

47

37

28

18th

9

* Polytetramethylene glycol with one

Molecular weight of about 2000.

Terephthaloyl-bis-caprolactam.

In each of the above approaches, polytetramethylene glycol, caprolactam, "Santowhite powder" and teraphthaloyl-bis-caprolactam are mixed at 100 ° C. As in Example 1, bromomagnesium pyrrolidone is added to the resulting mixture, the resulting mixture is heated to 120 ° C and molded in a form preheated to 100 ° C. The mold is heated to 160 ° C. as in Example 1 and held at this temperature for 30 minutes, after which the mold is opened, 6 seconds and the samples are removed. Table IV is a report on the mechanical properties of the compositions produced.

9

Table IV

628 360

Terpolymer

train

Strength, kg / cm2 yield point

% Elongation modulus at break

Tear resistance kg / cm2

print

Permanent deformation stress R.T. 100 ° C 25%

Impact resistance kg / cm / cm notch

A - 65% Polymeg

204

720

61

43

kB

B - 56% Polymeg

112

55

kB

C - 47% Polymeg

323

490

211

35

kB

D - 37% Polymeg

415

520

66

330

43

kB

E - 28% Polymeg

492

450

84

534

52

kB

F - 18% Polymeg

499

527

340

112

724

63

104.7

G - 9% Polymeg

626

647

89

105

1118

52

12.0

kB: sample did not break into two pieces.

Example 3

Seven different caprolactam-crosslinked-polypropylene- using the stock-glycol-terephthaloyl-bis-caprolactam terpolymers listed in Table V are produced in partial quantities.

Table V

material

A

B

C.

D

E

F

G

"Niax 61-58" *

229.5

196.4

163.3

130.3

98.1

64.1

31.0

Caprolactam

79.0

118.0

157.0

195.0

233.0

273.0

312.0

TBC

41.2

35.6

30.0

24.3

18.7

13.1

7.5

"Santowhite Powder"

0.7

0.7

0.7

0.7

0.7

0.7

0.7

BMP **

5.0

5.0

5.0

5.0

5.0

5.0

4.4

% By weight glycol

66

56

47

37

28

18th

9

Solution temperature

160

140

120

120

120

120

120

Initial mold temperature

160

140

110

110

110

120

120

* Multifunctional polypropylene glycol with a molecular weight of 2000. ® * Bromomagnesium pyrrolidone.

Each of the seven approaches is made according to the procedure of The properties are shown in Table VI below

Examples 1 and 2 performed with the exception that the reports.

Temperature and catalyst concentration varied as shown in the table above. 40

Table VI

Terpolymer

train

Tear

print

Blow

Strength, kg / cm2

strength

Permanent deformation

toughness

Flow

fracture

% Elongation modulus kg / cm2

stress

R.T.

100 ° C

kg / cm / cm

Point

in the event of breakage

25%

score

A - 66% niax

56

232

12th

46

23

66

B - 56% niax

112

302

17th

74

39

66

C - 47% niax

260

420

26

148

25th

66

D - 37% niax

400

402

39

246

47

66

E - 28% niax

506

557

67

450

62

53

F - 18% niax

429

485

305

98

745

58

66

G - 9% niax

654

598

52

120

1104

62

56

9.8

Example 4

Two caprolactam-polybutadiene-dio-isophthaloyl-bis-ca-prolactam terpolymers are prepared using the ingredient amounts shown in Table VII. 60

Table VII

Material, g AB

"Arco R-45 M" 165.3 131.8

Caprolactam 155.0 193.0

IBC "24.6 20.1

Table VII (continued)

Material, g A B

"Santowhite Powder" 0.8 0.8

% Glycol 48 38

Solution temperature 90 90

Initial mold temperature 100 100

Final temperature of the form 170 170

Polybutadiene diol with a molecular weight of 2000.

** Isophthaloyl-bis-caprolactam.

628 360

10th

The two terpolymers are prepared by the procedure of Examples 1 and 2 while maintaining the solution and mold temperatures given in Table VII.

The catalyst, bromagnesium pyrrolidone, is used at a concentration of 5 millimoles per mole of caprolactam. The properties are reported in Table VIII.

Table VIII

Terpolymer

train

Tear

print

Blow

Strength,

, kg / cm2

strength

Permanent deformation toughness

Flow

fracture

% Elongation modulus kg / cm2

Stress R.T.

100 ° C

kg / cm / cm

Point

in the event of breakage

25%

score

A - 48% Arco R-45M B - 38% Arco R-45M

148 211

230 212

703 1828

27 37

Example 5

Eight bis-caprolactam-polyethylene glycol-terephthaloyl-ca-prolactam terpolymers are prepared using the component amounts, temperatures of the solution and the mold listed in Table IX. The properties of the compositions are summarized in Table X.

Table IX

material

A

B

C.

D

E

F

G

H

"Carbowax 4000" *

229.1

241.2

141.7

60.0

46.6

13.8

9.0

4.2

Caprolactam

42.0

107.0

137.0

152.5

146.0

84.0

89.2

94.6

TBC

48.1

50.5

21.1

12.5

7.6

2.5

1.8

1.2

"Irganox 1010" **

0.9

0.9

0.4

"Santowhite Powder"

0.6

BMP *** (mmol / mol capro)

10.7

10.7

8.0

4.5

3.3

5.0

5.0

5.0

% By weight glycol

72

61

46

30th

23

14

9

4th

s Polyethylene glycol with a molecular weight of 4000.

: Tetrakis (methylene-3- (3'-5'di-tert-butyl-4'-hydroxyphenylpropionate) methane, antioxidant.: BMP - Bromomagnesium pyrrolidone.

Table X

Terpolymer

train

Strength, kg / cm2 yield point

% Elongation at break

module

Tear resistance kg / cm2

Pressure Impact Permanent Deformation Toughness Stress R.T. 100 ° C kg / cm / cm 25% notch

A - 72% carbowax

162

610

B - 61% carbowax

120

150

C - 46% carbowax

422

705

D - 30% carbowax

457

505

8 226

E - 23% carbowax

394

591

550

106

86

F - 14% carbowax

429

731

432

8 648

G - 9% carbowax

513

731

328

11 952

H - 4% carbowax

619

654

264

14 764

Examples 6

50 of the solution and the shape. The catalyst bromine

Two caprolactam-caprolactonediol-terephthaloyl-to-ca-prolactam terpolymers are used using the constituent amounts listed in Table XI, temperatures. Magnesium pyrrolidone is used in a concentration of 7.7 millimoles per mole of caprolactam. The properties of the compositions are reported in Table XII.

Table XI

material

A

B

"Niax PCP-0240" *

195.0

175.0

Caprolactam

69.0

141.0

TBC

36.3

33.6

"Santowhite Powder"

0.6

0.7

Solution temperature

90

100

Initial mold temperature

90

90

Final mold temperature

160

160

% By weight of polycaprolactone diol

65

50

Polycaprolactone diol

11

Table XII

628 360

Terpolymer

train

Tear

print

Blow

Strength, kg / cm2

strength

Permanent deformation toughness

Flow break c.c elongation modulus kg / cm2

Stress R.T. 100 ° C

kg / cm / cm

point at break

25%

score

A - 65% polycaprolactam B - 50% diol polycaprolactam

211 394

940 800

211 1055

47

Example 7

The purpose of this example is to determine the effect on the mechanical properties that the variation in the molecular weight of the polyol portion in the terpolymer has. The last three samples D, E and F show the effect of crosslinking on the same properties. The

Terpolymers are prepared using the ingredients and process conditions 15 listed in Table XIII. The bromomagnesium-pyrrolidone catalyst is used in a concentration of 5 millimoles per mole of caprolactam. The properties are summarized in Table XIV.

Table XIII

material

A

B

C.

D

E

F

Voranol type *

P1010

P2000

P4000

P4000

P4000

P4000

Voranol, g

155.2

163.3

168.5

159.6

138.8

126.4

"Pluracol 3030", g **

0

0

0

8.6

29.0

40.8

Caprolactam, g

143

157

166

165

164

163

IBC, g ***

52.3

30.2

15.8

16.6

17.9

19.4

% By weight triol

0

0

0

2.5

8.3

11.7

% By weight total polyol

44

47

48

48

48

48

* Polypropylene glycol with the specified molecular weight.

Polypropylene triol.

:: S: isophthaloyl-bis-caprolactam.

Table XIV

Terpolymer

train

Tear

print

Blow

Strength, kg / cm2

strength

Permanent deformation toughness

Flow

fracture

% Strain

Module kg / cm2

Stress R.T. 100 ° C

kg / cm / cm

Point

in the event of breakage

25%

score

A - 44% polyol

359

750

1336

42

B - 47% polyol

380

700

1687

42

155

C - 48% polyol

148

285

2672

41

169

D - 48% (2.5% triol)

176

357

2531

25th

176

E - 48% (8.3% triol)

190

337

1336

26

155

F - 48% (11.7% triol)

197

400

1336

22

127

Example 8

A reactor is charged with 106.3 g of caprolactam, 131.1 ml of triethylamine and 300 ml of chloroform. 45.8 g of phosphoryl chloride are added to the other reaction component within 45 minutes at a temperature of 25 to 30 ° C. The mixture is then stirred at room temperature for 7 hours, with a slight exothermic reaction taking place during the first 30 minutes. A portion of the mixture is filtered and the filtrate evaporated to give 67 g of a dark, semi-solid product. The product is further treated by slurrying in benzene, filtering and evaporating the filtrate; again slurrying in benzene and washing with water and subsequent evaporation, giving 17.3 g of an amber-colored, viscous product. The product phosphoryl-tris-caprolactam is used as an initiator in the following lactam-polyol-acylpolylactam formation.

A reactor is charged with 30 g of "Voranol 2000" (polyoxypropylene glycol with a molecular weight of 2011), 65.5 g of caprolactam and 4.48 g of phosphoryl-tris-caprolactam initiator. The latter is 0.67 g in excess of that by 30 g

50

55

60

65

“Voranol 2000” required molecular equivalents. 24 millimoles of bromagnesium pyrrolidone polymerization catalyst are added in 3 portions at a temperature of 160 to 165 ° C.

After 20 minutes the viscosity increases and the bottom part of the mixture becomes opaque and settles out as a solid polymer.

Example 9

A reactor is charged with 56.5 g (0.5 mol) of caprolactam, 71.1 ml of triethylamine and 400 ml of benzene. 24 g of phosgene are bubbled through the mixture at a temperature of 25 to 35 ° C. for 20 minutes. The mixture is stirred for 3 hours at a temperature of 40 to 60 ° C for 3 hours, filtered and the filtrate containing the product is washed twice with 100 ml of water and evaporated to give a mixture of semi-viscous liquid and crystals. Recrystallization from isopropanol gives 33.2 g of carbonyl-bis-caprolactam. The product is used as an initiator in the following lactam polyol acyl polylactam formation.

628 360

12th

A reactor is charged with 3 g (1.52 millimoles) of "Voranol 2000" and 6.5 g of caprolactam. The reactor is heated to 150 ° C for 15 minutes while bubbling with nitrogen to remove water. The mixture is cooled to 70 ° C. under nitrogen and 0.53 g (2.1 millimoles) of carbonyl-bis-caprolactam are added. The mixture is heated to 100 ° C to dissolve the initiator and cooled to 70 ° C before adding 0.3 millimoles of bromide magnesium pyrrolidone catalyst, which represents 10 millimoles of catalyst per mole of caprolactam. The catalyst is added to the mixture and the mixture is heated to 160 ° C. under nitrogen. After 5 minutes an increase in viscosity is observed and the bubbling of nitrogen is stopped. The lactam-polyol-acyl-polylactam terpolymer solidifies, but is still penetrable after 10 minutes. Complete solidification occurs 15 after 12 minutes.

Example 10

A reactor is charged with 75 g of "Voranol 2000" (polypropylene polyols with a molecular weight of 1974), 194 g of caprolactam and 1.25 g of "Flectol H" (polymerized 1,2-dihydro-20 2,2.4-trimethylquinoline) and heated in vacuo, to remove water. 17.1 g of isophthaloyl-bis-caprolactam are added and the mixture is heated again to remove water. A total of 50 g of caprolactam are distilled off during the two drying processes. The mixture is cooled to 65 ° C. and 13.95 g of catalyst (bromine magnesium caprolactam, 0.4 molar in caprolactam) are added and degassed for one minute. The mixture is poured into a sheet mold of 3 to 13 mm varying thickness heated to 100 ° C. The mold is heated to 30 160 ° C in 20 minutes and held at this temperature for 30 minutes. The lactam-polyol-polyacyllactam terpolymer hardens after the 30 minute period and the polymerized composition is removed.

The compositions of Example 10 and the following Examples 12 and 14 are tested to determine their mechanical properties, which are summarized in Table XV. The method and product of Example 10 are not according to the invention and are only presented for comparison purposes. Examples 11 and 12, as well as Examples 8, 40 and 9 are embodiments according to the invention.

Example 11

A reactor is charged with 37.5 g of “Voranol 2000”, 104 g of caprolactam and 0.62 g of “Flectol H” and heated to a temperature of 125 ° C. while 25 g of caprolactam are distilled off in vacuo. 8.35 g of phenylphosphonodi (2-keto-hexamethyIenimino) amide initiator are added to the mixture and stirred until dissolved. A catalyst solution, 8.39 ml of 2 molar chromium magnesium pyrollidone in N-methyl-pyrrolidone, which is 24 millimoles of catalyst per mol of caprolactam, is added to the mixture at 120 ° C. The mixture is poured into a foil mold heated to 160 ° C. The lactam-polyol-acylpolylactam terpolymer hardens in 5 to 6 minutes after insertion into the mold. The mold is opened 30 minutes after hardening and the polymerized composition is removed for testing.

Example 12

A vessel is charged with 37.5 g of "Voranol 2000", 103.8 g of caprolactam and 0.62 g of "Flectol H" and heated to 125 ° C. for 2 to 3 minutes while distilling off 25 g of caprolactam in vacuo. 8.35 g of phenylphosphonodi (2-keto-hexamethyleneimino) amide initiator are added to the mixture. A catalyst solution, 8.35 ml of 2 molar bromomagnesium pyrrolidone in N-methylpyrrolidone are added to the mixture under the same conditions as in Example 11. The product is used in the manner used in Examples 10 and 11,

45

50

55

60

> X

ü X> ci

H

J * G

S S

c> <

E c u a "SôH M

32 &

O o

^ 2

M »

C.

C w r-. ! Si --fa

"5.2 g OE a m

cn «M O G

UH Q.

<ü C *

H <tn

"S 4: * -S EgS" 5 * 2

00 .S * 0

cd vö tì X) ^

CÛ

c 3

â'SS

O g

E U

en 00

<N it

VO en en in co m

en (N

o in

"sf *

CS CM

in 00 it

Os es o

it

G &> a)

& VU

it

VO

W

bù

S

u

S

o «

ca tï 43 a

4-1 —M

Xi o CL

O S-

c / 2 Cy H-1 U

it m

00

ON C \ 10

VO VO

it it

"-1

en o o en

<N

O"

VO

irT

it

CL,

S «

O

a o.

-G Ctf o, *

71 1)

O Xi -G o

A o ~

>>

c j, j: -o

^ S §

o c

G

a>

m o \

00 o

"îfr o es o es

00 00 it o

it e cn m &

m it it

Oh m

a <

o g cr.

Xi cd d, X

tn <D O X!

Xi "

c 1 -a o ^ * G ^ S E

P-t "O S ca o c

"G o

1 §

E S

4 °

<u

00 1

a p s I

g <5 «S,

■ yy 00

• 2 1 as s * °

CÖ Ut

U CQ

: it O X O

og «o g §

_> v U

o>

O

Jrt O

.2 u ti

-5 5

JS O

•G

(U

O OÙ bû g o c

0 s:

00 .s

\ 0 -W

? I

■ ® ro »n -

13

628 360

Poured mold heated to 160 ° C. The lactam-polyol-acyl-polylactam terpolymer hardens in 9 minutes. The mold is opened 30 minutes after hardening and the finished polymerized composition is removed for testing.

For the related terpolymers of Examples 10, 11 and 12, as can be seen from Table XV, a distinguishable feature is the catalyst requirement of 4 millimoles per mole of caprolactam (Example 10) compared to the 24 millimoles per mole of caprolactam (Examples 11 and 12). This difference is attributable to the polyacyllactam initiator of Example 10 and the acylpolylactam initiator according to the invention of Examples 11 and 12. The rest of the comparison of physical properties shows similar, differing terpolymers, which is consistent with the reviews and formulations of the invention. is

Example 13

A batch of 325 g "Voranol 2000", 118 g caprolactam, 60.9 g isophthaloyl-bis-caprolactam and 2.5 g "Flectol 20 H" stabilizer is placed in a vessel provided with a stirrer, temperature controls, nitrogen inlet and vacuum distillation head. The mixture is heated in vacuo (<1 mm) to remove moisture by distilling 50 g of Caprolac

1

2nd

• 3

4th

5

6

7

** 250 ° C, 6800 g weight 1.3 mm opening

Example 14

A batch of 150 g "Voranol 2000", 119 g caprolactam, 29.2 g isophthaloyl-bis-caprolactam and 1.5 g "Flectol H" stabilizer are placed in a vessel equipped with a stirrer, temperature controls, nitrogen inlet and vacuum distillation head given. The mixture is heated in vacuo (<1 mm) to remove moisture by distilling 25 g of caprolactam. The resulting solution is cooled to 100 ° C and dissolved nitrogen is removed in vacuo, followed by addition of 1.7 ml of decyl alcohol and mixing the solution. The solution is catalyzed and poured into a vertical stainless steel foil press using a gear pump. The solution is at a rate of 876 ml / min. fed into the press. The catalyst solution (0.4 molar bromide magnesium caprolactam) is pumped in at a speed of 99 ml / min using a second gear pump. injected into the solvent stream, resulting in a catalyst concentration of 8 millimoles per mole of caprolactam.

Six lactam-polyol-polyacyllactam terpolymers are produced and cast in the same way, but the decyl alcohol is between 0 and 75%, and the temperatures of the solution and molding, as shown in Table XVII.

to remove tam. The vacuum is released under a nitrogen atmosphere and the solution is allowed to cool to 100 ° C. Dissolved nitrogen is removed in vacuo, followed by addition of 2.3 ml of decyl alcohol and mixing the resulting solution by stirring under nitrogen. The solution is catalyzed and poured into a vertical stainless steel foil press held at 100 ° C by means of a gear pump. The solution at a rate of 876 ml / min. fed into the press. The catalyst solution (0.4 molar bromagnesium caprolactam) is by means of a second gear pump at a speed of 103 ml / min. injected into the solvent stream, resulting in a catalyst concentration of 12 millimoles per mole of caprolactam. After casting, the press is heated to 160 ° C.

Seven lactam-polyol-polyacyllactam terpolymers are prepared and cast according to the above procedure, but the alcohol and alcohol concentration are varied as indicated in Table XVI. These experiments are identified in the table as batches 1 to 7, where in example 13 (batch 1) the decyl alcohol represents a 90% molar equivalent of the imide excess based on the molar equivalent of the hydroxyls present. The percentage of alcohol present is also representative of the% ester end groups in the resulting terpolymer.

lent to be varied. The results of Example 14 are listed in the table under Approach 2.

Example 15

A vessel equipped with a stirrer, temperature controls, nitrogen inlet and vacuum distillation head is charged with 90 g of polyethylene glycol (molecular weight about 3000), 219 g of caprolactam, 15.7 g of isophthaloyl-bis-caprolactam and 0.6 g of “Flectol H”. The mixture is heated in vacuo (<1 mm) to remove moisture by distilling 25 g of caprolactam. The vacuum is released through a nitrogen atmosphere and the resulting solution is cooled to 70 ° C. and degassed with the dissolved nitrogen. Cooling and degassing is followed by the addition of 0 to 4.8 ml of decyl alcohol and mixing of the solution. The catalyst, 3.3 ml of 2 molar bromagnesium pyrrolidone in N-methylpyrrolidone, is mixed with the solution and the mixture is poured into a vertical stainless steel press. The press is held at 100 ° C during the introduction of the solution and then heated to 160 ° C in 15 minutes and held at this temperature for a further 15 minutes.

Table XVI Effect of Decyl Alcohol

% Molar equivalence of alcohol to excess imide, calculated on molar equivalence of the polyol hydroxyl groups

train

Strength, kg / cm2

fracture

% Elongation at break

Module kg / cm2

Melt index ** dg / min.

90 65 0

129 160 115

1100 1200 800

302 211 134

54 37 0.09

90 50 40 0

Effect of 2-octanol

155 793

96 667

126 923

111 828

91 352 309 56

37.2 16.2 2.4 0.14

628 360

14

Table XVII

Effect of decyl alcohol, solution temperature and mold temperature

% * =

Dexyl alcohol

Solution temperature ° C

Molding temperature ° C

train

Strength, kg / cm2

fracture

% Elongation at break

module

Melt index dg / min.

1

2nd

3rd

4th

5

6

0 75 0 75 0 75

100 100 100 100 160 160

100-160 *

100-160 *

160

160

160

160

* As defined in example 13 and table 16. ** 100 ° C initial temperature, increased to 160 ° C.

273 337 164 337 181 316

730 720 470 770 470 745

1469 1174 352 1483 527 1329

0.09

3.4

0.3

3.8 0.2

3.9

Table XVIII presents the physical profiles of four terpolymers produced by the above method with decyl alcohol concentrations varying from 0 to 90%, where% alcohol is as defined in Example 13.

Table XVIII Effect of Decyl Alcohol

Decyl alcohol

%

Decyl alcohol ml

train

Strength, kg / cm2 break

% Elongation at break

module

Melt index dg / min.

1

2nd

3rd

4th

0 40 67 90

0

2.0 3.3 4.8

527 450 443 422

497 497 467

5343 6820 5625

0.01 0.3 0.83 2.5

Example 16

About 3000), 219 g of caprolactam, 0.6 g of "Flectol H", 15.7 of the terpolymers described in Table XIX are produced by the same method as in Example 15, g of isophthaloyl-bis-caprolactam, 0 to 2, 0 ml of decyl alcohol and, however, the following concentrations of components 3.3 ml of 2 molar bromagnesium pyrrolidone in N-methylpyr are used: 90.0 g of polyethylene glycol (molecular gerolidone.

Table XIX Effect of decyl alcohol

Decyl alcohol

%

Decyl alcohol ml

train

Strength, kg / cm: break

2nd

% Elongation at break

module

Melt index dg / min.

1

0

0

464

523

8437

1.5

2nd

5

0.4

415

410

9140

2.7

3rd

11

0.8

387

400

8437

3.0

4th

20th

1.05

394

410

7734

3.4

5

40

2.0

330

333

8015

4.5 •

A vessel equipped as in Examples 13 and 14 is charged with 75 g of "Voranol 2000", 180 g of caprolactam, 1.25 g of "Flectol H" and 17.1 g of isophthaloyl-bis-caprolactam. The mixture is heated in vacuo (<1 mm) to remove 60 moisture by distilling 50 ml of caprolactam. The resulting solution is cooled to 65 ° C. and 0.77 to 1.5 ml of 1-propanol or 1.1 to 1.37 ml of 2-propanol are added with stirring. The catalyst, 27.9 ml of 0.4 molar bromine magnesium caprolactam in caprolactam, is added to the solution and stirred for 1 minute; then the polymer solution is poured into the press according to Example 13 (pressing temperature 100 ° C.). The press turns from 100 within 20 minutes

17th

heated to 160 ° C and held at this temperature for 1 hour. The physical profiles of these terpolymers are compared in Table XX, which shows the effect of 1-propanol and 2-propanol.

Physical profiles, as explained in Tables XVI to XX, show the effects of some monohydric alcohols on the terpolymers. Improved melt index resulted from increased alcohol concentration, showing a decrease in the melt viscosity of the terpolymers in all batches. Improved strength and melt flow characteristics are achieved with e.g. B. the higher concentrations of poly-propylene glycols. The studies of the pre-

15

628 360

Table XX Effect of 1-propanol

1-propanol

1-propanol ml

train

Strength, kg / cm2 break

% Elongation at break

module

250 ° C

Melt index dg / min.

1

2nd

3rd

4th

50 75 90 100

0.77

1.1

1.35

1.5

342 313 352 309

472 173 505 176

7523 6960 5695 4359

0.1 0.2 0.8 1.4

75 90

Effect of 2-propanol 1.1 311 425

1.37 317 175

6328 7101

0.14 0.7

Sent influences of temperature and alcohol show the flexibility of alcohol-modified terpolymers having ester end groups, e.g. in the absence of the need for a two-stage polymerization. The statement “MoI% alcohol” in all examples and tables is based on

excess imide and corresponds approximately to the% prepolymer imide end groups, which are replaced by ester groups, and thus the% ester group terminations in the lactum-polyol-polyacyllactam or lactam-polyol-acylpolylactam ter-polymers.

Claims (20)

628 360 2nd 1. A process for the preparation of a terpolymer with ester and amide bonds between the monomer units, characterized in that (a) a lactam monomer of the formula: Y C = 0 (1) vnh y wherein Y represents an optionally substituted alkylene group with at least 3 carbon atoms, (b) a polyol and (c) a polyacyllactam or acylpolylactam of the formula: S- (A-R) ÌA'-N-Y-C] wherein A and A 'are an acyl group of the formula: 0 s 0 0 ÎÎ ?! t! ÎÏ -C-, -C-, -s-, tl 0 -s- or a divalent phosphorus-containing acyl group, the two free valences of which originate from one and the same pentavalent phosphorus atom which is bonded to an oxygen atom by a double bond, R denotes a (y + l) -valent hydrocarbon group, n represents 0 or 1 and y in the case of n = 0 the number 1 and in the case of n = 1 is an integer with a value of at least 1, in the presence of a basic lactam polymerization catalyst, the amount of polyol being 10 to 90% by weight of the polymerizable medium. 2. The method according to claim 1, characterized in that the amounts of the starting materials (b) and (c) are chosen so that the molar ratio between the N-acylated lactam rings supplied by (c) and the hydroxyl groups supplied by (b) is greater than 1: 1, and that by using a monofunctional alcohol which is also involved in the reaction, a terpolymer is prepared in which at least 0.1% of the total number of end groups of the polymer chains are carboxyl groups esterified with the monofunctional alcohol. 3. The method according to claim 1, characterized in that e-caprolactam is used as component (a). 4. The method according to claim 1, characterized in that the polyol is a polyalkylene glycol. 5. The method according to claim 4, characterized in that the polyalkylene glycol has a number average molecular weight of at least 1000. 6. The method according to claim 4, characterized in that the polyalkylene glycol is polyethylene, polypropylene or polytetramethylene glycol. 7. The method according to claim 1, characterized in that the polyol is polybutadiene diol. 8. The method according to claim 1, characterized in that the polyol is a polyester, e.g. Polycaprolactone diol. 9. The method according to claim 1, characterized in that A and A 'are carbonyl groups of the formula -CO-. Process according to claim 1, characterized in that the terpolymer is a block polymer, e.g. with the repeating AB block structure. 11. The method according to claim 1, characterized in that the lactam monomer (a) is caprolactam and the polyol (b) is a polyalkylene glycol. Process according to claim 1, characterized in that the catalyst is an alkali or alkaline earth lactam or a halogenated alkaline earth lactam, e.g. Bromomagnesium lactam. 13. The method according to claim 2, characterized in that the monofunctional alcohol is soluble in the lactam. 14. The method according to claim 13, characterized in that the molar amount of monofunctional alcohol used is 0.1 to 150% of the molar amount which results when one of the larger amount of N-acylated lactam rings expressed in moles, which in the amount of polyacyllactam or acylpolylactam used is included, which subtracts the smaller amount of hydroxyl groups, expressed in moles, which is contained in the amount of polyol used. 15. The method according to claim 1, characterized in that the acyl polylactam is an acyl bis-lactam. 16. The method according to claim 1, characterized in that the polyacyllactam is a bis-acyllactam, e.g. Therephthal-oyl- or isophthaloyl-bis-caprolactam. 17. The method according to claim 1, characterized in that one carries out the reaction of the lactam, polyol and polyacyllactam at a temperature of 90 to 190 ° C. 18. The method according to claim 1, characterized in that one carries out the reaction at an initial temperature of 70 to 100 ° C, which is increased to 150 to 180 ° C in the course of the polymerization. 19. A process for the preparation of a terpolymer with ester and amide bonds between the monomer units, characterized in that (i) a polyol and (ii) a polyacyllactam or acylpolylactam of the formula 2 given in claim 1 and then the resulting product and (iv ) a lactam monomer of the formula 1 given in claim 1 in the presence of a basic lactam polymerization catalyst, the amount of polyol IG up to 90% by weight, based on the sum of the weights of the reactants (i), (ii) and (iv), is. 20. The method according to claim 19, characterized in that the amounts of the starting materials (i) and (ii) are chosen so that the molar ratio between the N-acylated lactam rings supplied by (ii) and the hydroxyl groups supplied by (i) is greater than 1: 1, and that by using a monofunctional alcohol (iii) which is involved in the reaction, a terpolymer is prepared in which at least 0.1% of the total number of end groups of the polymer chains are carboxyl groups esterified with the monofunctional alcohol.